Chapter 5 : State of Matter II – Gases

Physical Properties of gases a. No definite shape b. No Definite Volume c. Can be easily compressed d. Rate of diffusion very high

Volume = f (Temperature, number of mole, Pressure)

5.1 Ideal gases 1. An ideal gases has the following features : a. The molecules has no volume (point particles) b. There are no intermolecular force between the molecules c. When the molecules collide, the collisions are perfectly elastic. This means that the molecules bounce apart when they collide with no loss in kinetic energy d. The particles are in rapid, random motion. They constantly collide with each other and the wall of the containing vessel. Thus pressure is due to the bombardment of these moving particles with the walls of the vessel. e. The average kinetic energy of the gas particles is a constant at a given temperature although the kinetic energy of a particle may vary from time to time

Law
Boyle’s Law

Definition
At a given temperature, the volume of a given mass of gas is inversely proportional to the pressure

Formula
PV = constant p1v1 = p2v2

Graph

Charles’s Law

At a given pressure, the volume of a given mass of gas is directly proportional to the absolute temperature

VαT

Avogadro’s Law

Equal volume of 2 gases at the same temperature and pressure contains the same number of molecules

2. General Gas Equation Value of R : pv R =nRT = pv/nT =(101325)(22.4 x 10-3)/(273) = 8.31 Jmol-1K-1

3. Dalton’s Law of Partial Pressure Definition : The total pressure of a mixture of gases is just the sum of the partial pressure of the constituent gases that it would exert if it were present alone.

4. Deviation from ideal gases a. Difference between ideal gases and real gases

b. Graphs represent deviation i. Different gases at the same temperature ii. Nitrogen gas at different temperatures

A real gas behave like an ideal gas under the following conditions 1. At low pressure. The molecules are then far apart. Hence, their volume is almost negligent compared to the volume of the container. The forces between the particles are virtually zero 2. At high temperature. The molecules move faster and so the attractive forces in between the particles are less significant STATE THE BEHAVIOUR OF THE NITROGEN GAS AT DIFFERENT TEMPERATURE AS COMPARED TO THAT OF AN IDEAL GAS. EXPLAIN WHY. 203K / 293K When pressure approaching zero, nitrogen gas behave like an ideal gas The volume occupied by the gas is large, the molecules are very far apart, the intermolecular force between molecules is not significant At low or moderately pressure, the nitrogen gas shows negative deviation from ideal gas The molecules are pushed closer and there exist attractive force between molecules Thus, the nitrogen gas is more compressible than ideal gas - volume of nitrogen gas is less than volume of ideal gas pv/RT for nitrogen gas is less than 1 – negative deviation from ideal gas At high pressure, the nitrogen gas shows positive deviation from ideal gas The molecules are pushed very close that there exists repulsive force between molecules Thus the nitrogen gas is less compressible than ideal - the volume of nitrogen gas is more than the volume of ideal gas

1000K -

Pv/RT for nitrogen gas is more than 1 – positive deviation

The nitrogen gas behaves like ideal gas at all pressure The kinetic energy of the molecules is very high to the extent that intermolecular force is not significant

A real gas shows the biggest deviation from ideality when a) Near condensing point b) High Pressure c) Low temperature

Phase Diagram
A) Maxwell-Boltzmann Distribution Curve 1. The molecules in a sample of gas are in constant motion often colliding on one another. Thus, the velocity of the molecules are spread over a wide range as shown by the Maxwell-Boltzmann Distribution Curve

a) Very few molecules with very low or very high velocity b) Most molecules with the most probable speed c) Area under the curve is the total number of molecules in the sample

2. At a higher temperature, a) The most probable speed increases ie the peak shift to the right b) Greater proportion of the molecules having high speed ie height of curve decreases h2 <h1 c) The total area under the two curves is the same

B) Vapour Pressure of Liquid

Vapour pressure – time curve

Vapour pressure – temperature curve

1. Explain, using kinetic theory, the effect of temperature on the vapour pressure of water • • • • • • Vapor pressure is the pressure due to the bombardment on the wall of the vessel by vapor molecules in equilibrium with its liquid at a fixed temperature Vapor pressure of water increases with increasing temperature When temperature increases, the kinetic energy of the vapor molecules increases Collisions of the vapor molecules on the wall of the vessel more frequent and with greater strength The kinetic energy of the water molecules also increases and thus more water molecules gain sufficient energy to escape as vapor – more molecules in the vapor phase Leading to higher frequency of collisions on the wall of vessel

2. At a fixed temperature, the vapor pressure of ethanol is higher than water. Explain • • Stronger H-bond between water molecules than between ethanol molecules More ethanol molecules than water molecules in the vapor phase

3. A volatile liquid is one with high saturated vapor pressure at room conditions 4. Boiling point is • • The temperature at which a liquid in equilibrium with its vapour At a particular pressure (vapor pressure = external pressure)

5. The molar enthalpy of vaporization is • • • The energy required To convert 1 mole of liquid to its vapor At its boiling point

** Normal boiling point is the temperature at which a liquid in equilibrium with its vapor at 101kPa ** The higher the external pressure, the higher is the boiling point ** A more volatile liquid has a lower boiling point

** It is used for the complete breakdown of the intermolecular force

Vapour Pressure of Solid 1. The vaporization of solid is called sublimation 2. Each solid has an equilibrium vapor pressure at a given temperature and the vapor pressure increases with increasing temperature (the increase is more than that of a liquid) 3. The melting point • • • Is the temperature At which a solid in equilibrium with its liquid At a particular pressure

C) Phase Diagram of Water (A phase is defined as a state of matter that is uniform throughout, not only in chemical composition but also in physical state. A phase diagram describes which phase is stable under particular conditions of temperature and pressure) Phase = f(T,p)

1. Each region represents conditions under which only one phase can exist 2. Each line represents conditions under which two phases can exist in equilibrium 3. TA shows the • • Variation of the saturated vapour pressure of liquid water with temperature Boiling point of water at different pressure

4. TB shows the • • Variation of the saturated vapor pressure of ice (solid water) at different temperature Sublimation temperature of ice with pressure

5. TC shows the melting point of ice or freezing point of water at different pressures. The line has a negative gradient showing that the melting point of ice decreases with increasing pressure. This is because melting involves decrease in volume. (This is predicted by Le Chatelier’s Principle. An equilibrium system consisting of water and ice at 1 atm will be at the normal melting point of 0oc. If the pressure on the water is now increased, there is a stress, which the system must relieve by shrinking in volume. It can shrink by converting some of the ice to water, hence melting is favoured. But heat is required to melt the ice and this heat must

come from the kinetic energy of the molecules. Consequently, there is a drop in temperature and the result is that solid ice and liquid water under increased pressure can only coexists at a lower temperature) 6. T is known as the triple point. This is the conditions of temperature and pressure when ice, liquid water and water vapour can coexist in equilibrium 7. A is the critical point. It shows the highest temperature at which water vapor can be condensed to liquid by increasing pressure (The kinetic energy of the molecules is so high that no matter how close the molecules are pushed together, the intermolecular force are not strong enough to hold the molecules together ie liquid cannot exist) 8. The molar enthalpy of fusion is the energy required to convert one mole of solid to liquid at its melting temperature. This energy is used to weaken the intermolecular force.

D) Phase diagram of Carbon Dioxide

1. The pressure at the triple point for carbon dioxide is higher than 1 atm. This means that a sample of solid carbon dioxide, at room conditions, will not melt but will sublime. This phenomenon is used in industry to freeze food such as ice cream (refrigerant) – it will not melt and wet the foodstuff. 2. In order to liquefy the carbon dioxide, increase the temperature of dry ice under a pressure higher than 5.2 atm 3. The line TC has a positive gradient ie the melting point of solid carbon dioxide increases with increasing pressure. This is because melting involves increase in volume. 4. Carbon dioxide in fire extinguisher is in the form of liquid

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